CN1057548C - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
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- CN1057548C CN1057548C CN94105231A CN94105231A CN1057548C CN 1057548 C CN1057548 C CN 1057548C CN 94105231 A CN94105231 A CN 94105231A CN 94105231 A CN94105231 A CN 94105231A CN 1057548 C CN1057548 C CN 1057548C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
A resin composition, excellent in a physical property balance between chemical resistance and impact strength, obtained by mixing at least one graft copolymer selected from the group consisting of a graft copolymer in which a copolymer rubber of an alkyl acrylate and a conjugated diene is used, and optionally with a rigid thermoplastic resin.
Description
The invention provides a kind of thermoplastic resin composition, it has excellent chemical-resistant resistance and impact resistance, and can be used as the resin component of the household electrical appliance transportation means that places the pharmaceutical chemicals environment of washing agent and machining oil such as living etc.
With ABS resin be representative rubber enhanced styrene resin, owing to it has the component that high resistance to impact shock is widely used as household electrical appliance launch vehicle etc.Therefore, these component may be exposed in the pharmaceutical chemicals sometimes.For example, the rosin products as this class of showerhead in wash stand and cocket handle and the bathroom often is exposed in the washing composition; Be used for automobile the resin component may with machining oil with remove that cerate contact and may be exposed in the fluon chlorofluorocarbon as the handle of water tank and the resin of door closure, it is the whipping agent of urethane during the production refrigerator thermal insulation material.Under such environment, these rosin productss usually ftracture or on its surface minute crack are arranged.
When the residual strain in moulded rubber enhanced styrene resin fat prod inside contacts with pharmaceutical chemicals by this product and part when disengaging, so-called environmental stress cracking phenomenon just occurs.And when this rosin products contacted with the pharmaceutical chemicals that low solubleness is arranged in resin, this phenomenon often can be observed.
There is a kind of improvement rubber to strengthen the method for the chemical proofing (tending to environmental stress cracking) of styrene resin (wherein crosslinked alkyl acrylate rubber is as rubber components) at present.The example that rubber strengthens styrene resin is by vinyl cyanide and the vinylbenzene AAS resin with crosslinked butyl acrylate rubber graft copolymerization acquisition.Yet because AAS resin has the low shortcoming of resistance to impact shock, its application in resin is restricted greatly.Improve the rubber content means though also can adopt as obtaining high resistance to impact shock, rosin products surface hardness that is obtained and rigidity step-down, thereby be easy to by scratch and deformation.Therefore this method is not preferred.Like this, obtaining to strengthen styrene resin at rubber all good aspect chemical proofing and the resistance to impact shock presses for.
The inventor has carried out research extensively and profoundly for the resin combination of developing a kind of physicals optimum balance in its chemical-resistant resistance and resistance to impact shock.The thermoplastic resin composition who found that its physicals optimum balance can be so that the mode that the content of rubber constituent drops on specified range in the thermoplastic resin composition with base stock, promptly at least aly be selected from following graft copolymer: the graft copolymer that wherein uses the copolymer rubber of alkyl acrylate and conjugated diolefine; Wherein use the elastomeric graft copolymer that makes by the inoculation rubber polymerization of alkyl acrylate and conjugated diene rubber and wherein use by alkyl acrylate and organopolysiloxane rubber and inoculate the rubber copolymerized rubber like graft copolymer that makes, mix with a kind of graft copolymer (wherein using conjugated diene rubber) and a kind of non-imposed rigid thermoplastic resin and obtain.
Therefore, the invention provides a kind of by with following base stock, i.e. graft copolymer (I) and graft copolymer (II) and following non-imposed component, i.e. rigid thermoplastic resin (III) mixing and the composition that makes:
(I) graft copolymer (I), it is the graft copolymer of at least a alkyl acrylate rubber and is selected from following graft copolymer (A), (B) and (C):
(A) graft copolymer (A), it is by the monomer mixture of unsaturated cyano compound that 20-80 part (weight) is contained 15-45% (weight) and 55-85% (weight) aromatic vinyl compound or contains 80-100% (weight) alkyl methacrylate and the monomer mixture of the alkyl acrylate of 0-20% (weight), (its median size is 0.15-0.5 μ m, and polymkeric substance (i) latex by will containing acidic group and non-imposed oxygen acid metal-salt (ii) are added to elastomeric polymkeric substance (a) latex (its gel content is greater than 70% (weight) and by the alkyl acrylate with 35-85% (weight) at the elastomeric multipolymer of gelling (a ') latex of 20-80 part (weight) (as solid ingredient), the conjugated diolefine of 15-65% (weight) and 0-20% (weight) can make with the monomer emulsion polymerization of these compound polymerizations) in make) exist graft polymerization down to make;
(B) graft copolymer (B), it is by 20-80 part (weight) being contained the monomer mixture of the aromatic vinyl compound of unsaturated cyano compound of 15-45% (weight) and 55-85% (weight), compounded rubber shaped polymer (b ') latex of 20-80 part (weight) (as solid ingredient) (its gel content greater than 70% (weight) and by 35-95% (weight) is contained alkyl acrylate and with the polymerisable monomeric monomer mixture of this alkyl acrylate, in the presence of conjugated diene rubber shaped polymer (b) latex of 5-65% (weight) (as solid ingredient), seeding polymerization makes) make under existing and
(C) graft copolymer (C), it is the monomer mixture by the aromatic vinyl compound of unsaturated cyano compound that 20-80 part (weight) is contained 15-45% (weight) and 55-85% (weight), graft polymerization makes in the presence of compounded rubber shaped polymer (c ') latex (its gel content makes at seeding polymerization in the presence of organopolysiloxane rubbery polymer (C) latex of 5-65% (weight) (as solid ingredient) greater than 70% (weight) and by 35 to 95% (weight) being contained alkyl acrylate and polymerisable therewith monomeric monomer mixture) of 20-80 part (weight) (as solid ingredient);
(II) graft copolymer, it is the monomer mixture by unsaturated cyano compound that 30-70 part (weight) is contained 15-45% (weight) and 55-85% (weight) aromatic vinyl compound, (its average footpath is 0.15-0.5 μ m at the elastomeric multipolymer of gelling (d ') latex of 30-70 part (weight) (as solid ingredient), polymkeric substance (d) latex that polymkeric substance (i) latex by will containing acidic group and non-imposed oxygen acid metal-salt (ii) are added to the conjugated diene rubber shape (its median size be 0.03-0.2 μ m and by with the conjugated diolefine of 70-100% (weight) and 0-30% therewith the monomer emulsion polymerization of copolymerization make) in make) have down that graft polymerization makes;
(III) rigid thermoplastic resin (III), it is selected from following monomer by at least 2 kinds of polymerizations and makes: unsaturated cyano compound, aromatic vinyl compound, unsaturated ester and maleimide compound; Wherein the described thermoplastic resin composition of 100% (weight) rubbery polymer that contains the rubbery polymer and 100% (weight) of 15-30% (weight) contains the alkyl acrylate ester units of 30-85% (weight).
Below explain in detail the present invention.
For the alkyl acrylate type rubbery copolymer (a) of graft copolymer (A) is provided, by the alkyl acrylate with 35 to 85% (weight), the conjugated diolefine of 15 to 65% (weight) and 0 to 20% (weight) can make with the monomer emulsion polymerization of these compound copolymerization.
Be used for herein alkyl acrylate and refer to that its alkyl has the alkyl acrylate of 1 to 12 carbon atom or vinylformic acid aryl ester such as phenyl and benzyl group is arranged.The example of preferred acrylate is a n-butylacrylate, acrylic acid-2-ethyl polyhexamethylene, ethyl propenoate etc.Can use in these compounds one or at least two.In addition, (each has such as vinylformic acid Racemic glycidol alcohol ester acrylate, vinylformic acid-2-hydroxyethyl ester, the functional group of vinylformic acid tetrahydroxy furfuryl group ester and vinylformic acid dimethyl aminoethyl ester) can mix use with above-claimed cpd, as long as institute's consumption only reaches 30% (weight).
The example of conjugated diolefine is a 1,3-butadiene, isoprene, chloro pentadiene etc.In these compounds, 1,3-butadiene is preferred.
In addition, can be with the monomeric example of alkyl acrylate copolymerization, polyfunctional monomer such as allyl acrylate, allyl methacrylate(AMA), Vinylstyrene, Ethylene glycol dimethacrylate, the diacrylate butanediol ester, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane diacrylate, tetramethylol methane tetraacrylate, insatiable hunger cyano compound such as vinyl cyanide, aromatic ethenyl compound such as vinylbenzene, alkyl methacrylate such as methyl methacrylate and monofunctional monomer, for example unsaturated carboxylic acid such as methacrylic acid.Can use these compounds one or at least two.When the amount of used conjugated diolefine is fewer, use at least a polyfunctional monomer usually.
Consider the balance of performance between resistance to impact shock and the chemical-resistant resistance, the amount of the alkyl acrylate in the alkyl acrylate rubber-like multipolymer (a) is fixed on 35 to 85% (weight).Content is not preferred less than 35%, because resin combination chemical resistance variation.Then can damage resistance to impact shock greater than 85%, consider resistance to impact shock, rubbery copolymer (a) needs the gel content greater than 70% (weight).
The median size of rubbery copolymer (a) is preferably 0.03 to 0.2 μ m.Rubbery copolymer (ii) condenses by the metal-salt that adding contains acid groups copolymer emulsion (i) and non-imposed oxygen acid, its mean particle size is 0.15 to 0.5 μ m, preferred 0.2 to 0.4 μ m, the rubber of big particle diameter can stably obtain at short notice with coagulation.
Though preferred rubber shape multipolymer (a) borrows coagulation all should become the multipolymer that condenses (a '), such variation is rarely found usually.Yet even still have the particle that do not condense on a small quantity (rubbery copolymer that condenses (a)), the physicals of resin combination of the present invention does not still have any problem.
The copolymer emulsion (i) that contains acid groups can be by obtaining a mixture letex polymerization, described mixture contain 3 to 40% at least aly be selected from following unsaturated acid: vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, toxilic acid, fumaric acid, styracin, Sorbic Acid and p styrene sulfonic acid; At least a alkyl acrylate of 97 to 35% (weight), its alkyl have 1 to 12 carbon atom; With 0 to 40% (weight) can with the another kind of monomer of these compound copolymerization.In these multipolymers, typical example is the multipolymer of vinylformic acid and butyl acrylate.
Be used for oxygen acid of the present invention metal-salt (ii) and refer to that at least one is selected from following oxysalt: an alkali metal salt of oxygen acid, alkaline earth salt, zinc salt, nickel salt and aluminium salt, described oxygen acid each therein the heart element that is selected from the IIIA of periodictable second and period 3 to VIA family is arranged.Concrete oxygen acid metal-salt example (ii) is the vitriol of metal such as potassium, sodium, magnesium, calcium, zinc and aluminium, nitrate and phosphoric acid salt.Preferred example is a vitriolate of tartar, sodium sulfate and sodium phosphate.The oxygen acid metal-salt (ii) is added into the form of the aqueous solution.
The add-on of condensing agent is as described below.Containing acidic group copolymer emulsion (i) is added in the alkyl acrylate rubbery copolymer (a) of 100 parts of (weight) (as solid ingredients) with 0.5 to 8 part of (weight) (as solid ingredient).When mixing uses the oxygen acid metal-salt (ii), contain the acidic group copolymer emulsion (i) and the oxygen acid metal-salt aqueous solution (ii) and add with the amount of 0.5 to 5 part of (weight) (as solid ingredient) and 0.05 to 12 part of (weight) (as solid ingredient) respectively.
Agglomerative rubbery copolymer (a of Huo Deing like this
1) latex carries out graft polymerization successively.Graft polymerization is by a monomer mixture (containing the unsaturated cyano compound of 15 to 45% (weight) and the aromatic ethenyl compound of 55 to 85% (weight)) or a monomer mixture (containing the alkyl methacrylate of 80 to 100% (weight) and the alkyl acrylate of 0 to 20% (weight)) with one 20 to 80 parts of weight, at 20 to 80 parts of (weight) (as solid ingredients) rubbery copolymer (a that condenses
1) latex carries out polymerization under existing.
The monomer mixture usage quantity can form the outward appearance of thick particle or infringement resin combination in the curing schedule of graftomer less than 20 parts (weight); therefore not preferred; the consumption that does not also preferably surpass 80 parts (weight) in addition; because need use a large amount of emulsifying agents, cause during hot-work resin combination painted for carrying out stable graft polymerization.
The example that is used for the unsaturated cyano compound of graftomer is a vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, Maleic nitrile, flumaronitrile etc.In these compounds, preferably use vinyl cyanide.
The example of aromatic ethenyl compound is a vinylbenzene, alpha-methyl styrene, and neighbour-vinyl toluene, p-methylstyrene, 2, the 4-dimethyl styrene, right-ethyl styrene, right-t-butyl styrene, halogenated styrenes etc.In these compounds, preferably use vinylbenzene and alpha-methyl styrene.
Unsaturated cyano compound consumption is 15 to 45% (weight), preferred 20 to 35% (weight), and the aromatic vinyl compound consumption is 55 to 85% (weight), preferred 65 to 80% (weight).
Unsaturated cyano compound consumption should not be less than 15% (weight), because this can damage resistance to impact shock.Its consumption should not surpass 45% (weight) because this may damage moldability or heat decoloring takes place.
The alkyl methacrylate that is used for graft polymerization is that a straight chained alkyl (its carbonatoms is 1 to 8) or cycloalkyl are arranged, or phenyl, benzyl, glycidyl, the methacrylic ester of 2-hydroxyethyl.Can use or at least two in these esters.In above-mentioned ester, the preferable methyl methyl acrylate.
For improving the thermolysis stability of resin combination of the present invention during mediating, in 100% (weight), replace up to the most handy alkyl acrylate of 20% (weight) alkyl methacrylate.
The preferred example that is used for alkyl acrylate herein is methyl acrylate or ethyl propenoate.
Conventional letex polymerization can be fitted and in graft polymerization.An available step of one of following method or at least two steps carry out: monomer adds and polymerization in batches; At first add partial monosomy, remaining monomer splashes into; Whole monomer splashes into and arbitrarily carries out polymerization.When number of steps was at least 2, although monomeric type and composition can change in each step, these methods still can be carried out.The graft copolymer of Huo Deing solidifies with known method like this, and through such as dehydration, washing and drying step, obtains graft copolymer (A).
The compounded rubber shaped polymer (b ') that provides for graft copolymer (B) be by with the monomer mixture of 35 to 95% (weight) (contain alkyl acrylate and can with the monomer of this alkyl acrylate copolymerization), seeding polymerization in the presence of conjugated diene rubber shaped polymer (b) latex of 5 to 65% (weight) (as solid ingredient) and getting.
When the polymkeric substance (b) of conjugated diene rubber shape drops on outside the above-mentioned scope, the resistance to impact shock of resin or chemical resistance variation.Not preferred thus such consumption.
The conjugated diene rubber shaped polymer (b) that is used for this paper be by the conjugated diolefine of at least 50% (weight) and at the most 50% (weight) can be with the preparation of the monomer of polymerization of conjugated dienes.The exemplary of conjugated diolefine is a 1,3-butadiene, but the monomeric example of isoprene and the copolymerization of chloro pentadiene is unsaturated cyano compound such as vinyl cyanide and aromatic ethylene based compound such as vinylbenzene.The preferred example of conjugated diene rubber shaped polymer is a polyhutadiene, acrylonitrile butadiene copolymer rubber, styrene-butadiene copolymer rubber etc.In these materials, polyhutadiene most preferably.These materials make by letex polymerization.
Conjugated diene rubber shaped polymer (b) latex preferably is big particle, and its granularity is 0.2-1.0 μ m.Though under low speed, can meet the demands by this macrobead rubber that seeding polymerization makes, preferably the macrobead rubber that makes with gelatinization process through sufficiently long time, several steps of process.That is, be to add copolymer emulsion (i) and the metal-salt non-imposed, that be used for the oxygen acid of graft copolymer (A) that contains acidic group in the alkaline rubber latex of 0.03-0.15 μ m to granularity, can stablize and make conjugated diene rubber polymkeric substance (b) effectively.For obtaining having the agglomerative rubber of above-mentioned granularity, require the pH of this alkaline rubber latex should be at least 9, and should use have a high content of unsaturated acid contain the acid groups copolymer emulsion.Be not that all alkaline rubbers can be converted into gelling rubber by gelation, usually can residual a certain amount of not agglomerative alkaline rubber, therefore, gained gelling rubber has two kinds of size-grade distribution, and the mean particle size of conjugated diene rubber is preferably 0.2-1.0 μ m.But, do not consider not agglomerative alkaline rubber part if only consider volume particle size gelling rubber part, then mean particle size is preferably 0.4-1.2 μ m.
In the presence of conjugated diene rubber shaped polymer (b) latex, by contain alkyl acrylate and can with the seeding polymerization reaction of the monomeric monomer mixture of its copolymerization, make compounded rubber (b ') latex.
The example of alkyl acrylate is and is used for similarly acrylate of graft copolymer (A).The monomeric example that can close with alkyl acrylate copolymer is monofunctional monomer such as vinyl cyanide, vinylbenzene, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl and methacrylic acid dodecyl ester and multiple functional radical monomer linking agent described as follows and graft crosslinking agent.Consider resistance to impact shock, in these compounds, preferably combination is used linking agent and graft crosslinking agent.
The example of linking agent is Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, dimethacrylate 1,3 butylene glycol ester, dimethacrylate 1,4-butanediol ester etc.The example of graft crosslinking agent is allyl methacrylate(AMA), triallyl cyanurate, triallyl isocyanurate etc.Can use these linking agents and graft crosslinking agent separately, perhaps use at least two mixture.
Based on containing the monomer mixture that main component is an alkyl acrylate, total consumption of the graft crosslinking agent of linking agent is preferably 0.01%-10% weight.The monomeric consumption of monofunctional is preferably 0-30% weight.
The typical example of monomer mixture that is used for seeding polymerization contains the mixture of alkyl acrylate, 0.07%-4.97% (weight) linking agent and the agent of 0.03%-4.98% (weight) graft crosslinking that 95%-99.95% (weight) is generally butyl acrylate for (total amount is 100% (weight)).
In addition, consider resistance to impact shock, require the gel content of compounded rubber shaped polymer (b ') should be greater than 70% (weight).
In the presence of conjugated diene rubber polymkeric substance (b), the example of seeding polymerization method of monomer mixture that contains main component and be alkyl acrylate is as follows: Yi Bian drip monomer mixture, Yi Bian carry out polyreaction; Soak the alkaline rubber shaped polymer with monomer mixture in advance, add polymerization starter etc. then and carry out polymerization; Carry out the polymeric operation later on monomer mixture immersion alkaline rubber shaped polymer and repeat several times continuously, and change the composition of monomer mixture in each step; Or the like.In these methods, preferred method is; Soak the alkaline rubber shaped polymer with monomer mixture earlier, with post polymerization.In addition, for improving the stability of polyreaction, in the seeding polymerization process, also can add emulsifying agent.But its consumption should be as far as possible little.
Seeding polymerization makes the conjugated diene rubber polymkeric substance (b) of core do not inoculated sometimes, and only to have produced by being derived from main component be the rubber polymer product that the monomer mixture unit of alkyl acrylate is formed.The gained thermoplastic resin composition can not influence target capabilities of the present invention.But, when the by product amount increases, may harm the outward appearance of moulded parts prepared therefrom.Therefore, the amount of above-mentioned by product is as far as possible for a short time is preferred.
Compounded rubber shaped polymer (b ') latex of above-mentioned preparation carries out graft polymerization subsequently, in the presence of 20 to 80 weight part (as solid ingredient) compounded rubber shaped polymer (b ') latex, make 20 to the 80 weight parts monomers mixture graft polymerizations that contain unsaturated cyanogen compound of 15%-45% (weight) and 55%-85% (weight) vinyl aromatic compound, carry out graft polymerization reaction.
Identical as in the monomeric unsaturated cyanogen compound of graftomer and vinyl aromatic compound kind and consumption and graft polymerization procedure and the graft copolymer (A).The latex that so makes carries out as curing, dehydration, washing and drying treatment, makes graft copolymer (B).
On the other hand, organopolysiloxane rubbery polymer (C) is the rubbery polymer that is prepared by organo-siloxane, linking agent and non-imposed graft crosslinking agent.The example of organo-siloxane is the various ring compounds that are at least the member of unit ring, is preferably 3-6 unit ring.Its object lesson is hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotrisiloxane, octaphenyl cyclotetrasiloxane.Can use these compounds separately, also can use both mixtures at least.
Linking agent be exemplified as trifunctional or four functional silicomethane type linking agents, as trimethoxy methyl-silicane, triethoxy phenyl silicomethane, tetramethoxy-silicane, tetraethoxy-silicane, four positive propoxy silicomethanes and four butoxy silicomethanes.Preferred especially four functional crosslinkers and preferred especially tetraethoxy-silicane wherein.The consumption of linking agent accounts for the 0.1-30% (weight) of poly-organic first silicone rubber shaped polymer (C).
Can form unitary compound shown in the following formula or other material and can be used as the graft crosslinking agent
CH
2＝C-COO-(CH
2)p-SiR
1 nO
(3-n)/2 (1)，
|
R
2
CH
2＝CH-SiR
1 nO
(3-n)/2 (2)
HS-(CH
2) p-SiR
1 nO
(3-n)/2(3) R in the formula
1Be methyl, ethyl, propyl group or phenyl, R
2Be hydrogen atom or methyl, n is 0,1 or 2, and P is 1 to 6 integer, owing to can form the polysiloxane grafted efficient height of unitary (methyl) shown in the formula (I) acrylic, so can form effective grafted chain, can advantageously improve shock resistance.In addition, the methacrylic acid radical siloxane be particularly preferred, can form the unitary compound of formula (I).The typical case of methacrylic acid radical siloxane is Beta-methyl acrylic ethyl dimethoxy-methyl silicomethane, γ-methacrylic acid group propyl group methoxyl group dimethylsilane, γ-methacrylic acid group propyl group dimethoxy-methyl silicomethane, γ-methacrylic acid propyl trimethoxy silicomethane, γ-methacrylic acid group propyl group oxyethyl group diethylsilane, γ-methacrylic acid group propyl group diethoxymethyl silicomethane, δ-methacrylic acid group butyl diethoxymethyl silicomethane etc.The consumption of graft crosslinking agent accounts for the 0-10% weight of organopolysiloxane rubber polymer (C).
The mean particle size preferable range of organopolysiloxane rubbery polymer (C) latex is 0.08-0.6 μ m.When mean particle size was lower than 0.08 μ m, the moulded parts shock resistance that resin combination makes was poor.In addition, when mean particle size surpassed 0.6 μ m, the moulded parts that resin combination makes was except that the shock resistance difference, and surface property is also poor.Therefore, mean particle size can not exceed above-mentioned scope.
Though, for example available U.S No.2,891,920 and 3,294,725 disclosed methods prepare organopolysiloxane rubbery polymer (C) latex, but preferably use homogenizer etc., in the presence of sulfonic acid class emulsifying agent, prepare them by shear-mixed organo-siloxane, linking agent and non-imposed graft crosslinking agent and the mixture solution of water as alkyl benzene sulphonate (ABS) or alkylsulphonic acid.Alkyl benzene sulphonate (ABS) is more suitable because it can be simultaneously as the emulsifying agent and the polymerization starter of organo-siloxane.In polymerization process, be used in combination the metal-salt of alkyl benzene sulphonate (ABS), the metal-salt of alkylsulphonic acid etc., can stablize the polymkeric substance that keeps in the graft polymerization process, thereby be preferred.
In coming by the aqueous solution that adds alkali such as sodium hydroxide, potassium hydroxide or yellow soda ash and organopolysiloxane rubber polymer (C) latex, and be used for the monomer that the seeding polymerization main component is an alkyl acrylate subsequently.
In the presence of 5-65% (weight solids component) organopolysiloxane rubbery polymer (C) latex, seeding polymerization 35-95% (weight) contain alkyl acrylate and can with the monomeric monomer mixture of its copolymerization, prepare compounded rubber shaped polymer (C ') latex.
The alkyl acrylate that is used for seeding polymerization with can be with described in the monomeric kind of its copolymerization and consumption and seeding polymerization method and the graft copolymer (B) identical.
Consider resistance to impact shock, the gel content of compounded rubber shaped polymer (C ') is preferably greater than 70% (weight).
Compounded rubber shaped polymer (C ') latex that so makes is used for graft polymerization subsequently.In the presence of compounded rubber shaped polymer (C ') latex of 20-80 weight part, graft polymerization 20-80 weight part contains the monomer mixture of the vinyl aromatic compound of unsaturated cyanogen compound of 15-45% (weight) and 55-85% (weight), carries out graft polymerization.
Identical as in the kind of the monomeric unsaturated cyanogen compound of graft polymerization and vinyl aromatic thing and consumption and graft polymerization procedure and the graft copolymer (A).The latex that so obtains is carried out as curing, dehydration, washing and drying treatment, prepare graft copolymer (C).
Conjugated diene rubber multipolymer (d) latex that is used for graft copolymer (II) is can to prepare with the monomer of its copolymerization by letex polymerization 70-100% (weight) conjugated diolefine and 0-30% (weight).
The typical case of conjugated diolefine used herein is 1,3-butadiene, isoprene and chloro pentadiene.Consider resistance to impact shock, the consumption of conjugated diolefine is at least 70% (weight).
Can with the monomeric unsaturated cyano compound such as the monomers such as vinyl cyanide, vinyl aromatic compound such as vinylbenzene, alkyl methacrylate such as methyl methacrylate, unsaturated carboxylic acid such as methacrylic acid of being exemplified as of conjugated diolefine copolymerization.Can use these compounds by monomer, or use both mixtures at least.
The preferred exemplary of conjugated diene rubber shaped polymer (d) is polybutadiene rubber, acrylonitrile butadiene copolymer rubber and styrene-butadiene copolymer rubber.
The mean particle size preferable range of conjugated diene rubber multipolymer (d) latex is 0.03-0.2 μ m.The metal-salt that contains acidic group copolymer emulsion (i) and non-imposed oxygen acid by adding (ii), the mean particle size range of agglomerative conjugated diene rubber multipolymer (d) latex is 0.15-0.5 μ m, be preferably 0.2-0.4 μ m, (i) and kind (ii) and consumption explanation in explaining graft copolymer (A).This gelation can be stablized gelling rubbery copolymer (d ') latex that preparation has volume particle size and suitable resistance to impact shock at short notice.
Agglomerative rubbery copolymer (d ') latex is used for graft polymerization subsequently.In the presence of 20 to 80 weight part agglomerative rubbery copolymer (d ') latex (solids component), by at least a monomer that is selected from unsaturated cyano compound, vinyl aromatic compound and unsaturated ester of graft polymerization 20-80 weight part, carry out graft polymerization.
The monomeric preferred exemplary that is used for graftomer is described those monomers when explaining graft copolymer (A).(A) is similar to graft copolymer, can adopt any known emulsion polymerisation process to carry out graft polymerization.The graft copolymer latex that so makes is solidified with currently known methods, carry out handling, prepare graft copolymer (II) as dehydration, washing and exsiccant.
Be selected from the monomer of unsaturated cyano compound, vinyl aromatic compound, unsaturated ester and maleimide compound by at least two kinds of copolymerizations, prepare and be used for rigid thermoplastic resin of the present invention (III).
The typical case of unsaturated cyano compound is vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, propane dinitrile, succinonitrile etc.Vinyl cyanide wherein is a preferred exemplary.Vinyl aromatic compound be exemplified as vinylbenzene, alpha-methyl styrene, a vinyltoluene, to vinyltoluene, to ethyl styrene, to t-butyl styrene, 2,4-dimethyl styrene, halogenated styrenes etc.Vinylbenzene wherein and alpha-methyl styrene are typical cases.Unsaturated ester be exemplified as methacrylic ester such as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester etc.Methyl methacrylate wherein is a typical case.Being exemplified as maleimide, having C of maleimide compound
1-C
12The N-alkyl maleimide of alkyl, N-phenylmaleimide and on phenyl ring, have at least one to be selected from C
1-C
6Alkyl, halogen atom, C
1-C
4The substituent derivative of alkoxyl group, phenyl, carboxyl, nitro, amido and cyano group.N-phenylmaleimide wherein and N-cyclohexyl maleimide are typical cases.
Though prepare this rigid thermoplastic resin (III) with at least two kinds of above-mentioned monomers, preferably it contains at least a unsaturated cyano compound unit.The concrete representation example of rigid thermoplastic resin (III) is acrylonitritrile-styrene resin, vinyl cyanide-α-Jia Jibenyixigongjuwu, acrylonitrile-styrene-methylmethacrylate copolymer, acrylonitrile-styrene-N-phenylmaleimide multipolymer etc.Example is following multipolymer more specifically: contain 20-45%, preferred 25-40% (weight) acrylonitrile unit, 55-80%, preferred 60-75% (weight) styrene units or the unitary multipolymer of alpha-methyl styrene; Contain 10-40% (weight) acrylonitrile unit, 30-50% (weight) styrene units and 30-50% (weight) methyl methacrylate units (total amount: multipolymer 100% weight); With contain 10-40% (weight) acrylonitrile unit, 40-80% styrene units and 5-40% (weight) N-phenylmaleimide unit or the unitary multipolymer of N-cyclohexyl maleimide.
Can use a kind of rigid thermoplastic tree group (III) or at least two kinds to be used in combination.Though be not particularly limited the preparation method of rigid thermoplastic resin (III), preferred employing can make the method that preferably realizes its performance resin (III).
By mixing the rigid thermoplastic resin (III) of essential composition graft copolymer (I), graft copolymer (II), non-epistasis, prepare the thermoplastic resin composition who invents, wherein graft copolymer (I) is at least a graft copolymer (A), (B) and the graft copolymer (C) of being selected from.Graft copolymer (I) mainly is in order to make this resin combination have chemical resistance.Graft copolymer (II) is main relevant with the resistance to impact shock of resin combination.
The blending ratio of graft copolymer (I), graft copolymer (II) and rigid thermoplastic resin (III) should make rubbery polymer content among the thermoplastic resin composition in preferable range.Promptly, blending ratio is as follows: in the 100% weight thermoplastic resin composition, the content of rubbery polymer is 15-30%, is preferably 20-28% (weight) that in 100% (weight) rubber polymer, vinylformic acid mono alkyl ester unit content is 30-85% (weight).
When the content of wherein rubbery polymer becomes when being less than 15% (weight), this thermoplastic resin composition's resistance to impact shock and chemical resistance variation, this content range is not preferred.In addition, when this content surpassed 30% (weight), surface hardness and rigidity descended, and therefore, its application is restricted, and this content range is not preferred.In addition, become when being less than 30% (weight) its chemical resistance variation when the acrylic acid alkyl fat in the rubbery polymer.When this content surpasses 85% (weight), its shock resistance variation.Therefore, above-mentioned content range is not preferred.
According to the present invention, from only containing the resin combination of graft copolymer (I) or graft copolymer (I) and rigid thermoplastic resin (III), just may obtain such thermoplastic resin composition, wherein satisfy the rubbery polymer content in the concrete resin combination, and satisfy the unitary content of alkyl acrylate in the rubbery polymer.Yet, though these thermoplastic resin compositions have good chemical resistance, their how many variation of shock resistance.Therefore, their application is restricted.In order to obtain having the thermoplastic resin composition of fabulous shock resistance characteristic, used rubbery polymer content must increase.As mentioned above, the increase of this content is worthless to the surface hardness and the rigidity of this resin combination.Therefore, in order to obtain having the resin combination of fabulous resistance to impact shock, it is essential mixing graft copolymer (II), for the effect that obtains fully to mix graftomer (II), preferably mixes at least 5 weight parts.
Graft copolymer (I), graft copolymer (II) and rigid thermoplastic resin (III) mix with bitubular blending machine, Henschel mixing tank or similar devices usually.In mixing process, also can add additive such as various stablizer, lubricant, softening agent, release agent, dyestuff, colorant, mineral filler, fine metal particle and static inhibitor.The mixture of gained is kneaded by screw extrusion press, mixing roll or similar devices fusion, and with a tablets press granulation.
Embodiment
With reference to following examples, the present invention is described in more detail, but should points out, content of the present invention is not limited to these embodiment.In addition, " part " in embodiment and comparative example is meant weight part.In addition, the mean particle size of rubbery polymer latex is to fix this rubbery polymer latex with perosmic anhydride etc., takes a picture with transmission type microscope, and measures this image and obtain.In addition, record its gel content by following process.
Under 30 ℃ the exsiccant rubbery polymer was soaked in toluene 24 hours, and filter through one 200 order (mesh) sieve.Residue on the dry sieve, the weight ratio of exsiccant rubber polymer just can calculate when gel that obtains like this and beginning:
Synthesizing of alkyl acrylate rubbery copolymer (a-1)
50 parts of n-butyl acrylates
50 parts of 1,3-butadienes
0.2 part of diisopropyl benzene hydroperoxy-
0.4 part of uncle's dodecyl mercaptans
1 part of potassium oleate
1 part of the sodium salt of N-lauroyl sarcosine
0.5 part of rongalite
195 parts of distilled water
In above-mentioned composition, other material of all except that 1,3-butadiene is all removed oxygen with nitrogen.Therefore, the reaction of back can not blocked by oxygen basically.With the above-mentioned all substances 50 liters of autoclaves of packing into, and under vigorous stirring, be heated to 55 ℃, add following mixture again.55 ℃ of following polymerizations 8 hours, obtain a kind of alkyl acrylate rubbery copolymer (a-1) latex, the monomer whose transformation efficiency is 98%, granularity is 0.07 μ m, has measured its gel content, is 82% (weight).
Disodium EDTA. 0.012 part of dihydrate
Ferrous sulfate. 0.004 part of heptahydrate
5 parts of distilled water
Synthesizing of alkyl acrylate rubbery copolymer (a-2)
99 parts of n-butyl acrylates
0.8 part of allyl methacrylate(AMA)
0.2 part of Vinylstyrene
0.02 part of diisopropyl benzene hydroperoxy-
1.2 parts of potassium oleates
0.8 part of the sodium salt of N-lauroyl sarcosine
0.4 part of rongalite
198 parts of distilled water
With pack into one 50 liters polymerization reaction kettle of above-mentioned composition, replace oxygen in the still fully with nitrogen, and content is heated to 50 ℃.Add following mixture then.50 ℃ of polymerizations 5 hours, obtain a kind of alkyl acrylate rubbery copolymer (a-2) latex, monomer conversion is 98%, and the granularity of latex is 0.14 μ m, and gel content is 78% (weight).
The disodium salt disodium salt. 0.000015 part of dihydrate
Ferrous sulfate. 0.000005 part of heptahydrate
2 parts of distilled water
Synthesizing of conjugated diene rubber shape multipolymer (d-1)
100 parts of 1,3-butadienes
0.2 part of diisopropyl benzene hydroperoxy-
0.5 part of uncle's lauryl mercaptan
1 part of potassium oleate
Rhodium acid potassium (the potassium rhodinate) 1 part of disproportionation
Dextran 10 .3 part
0.18 part of anhydrous sodium sulphate
0.02 part in sodium hydroxide
195 parts of distilled water and
Trisodium phosphate. 0.5 part of decahydrate
Ferrous sulfate. 0.005 part of heptahydrate
5 parts of distilled water
Be used in the step that is adopted in alkyl acrylate rubbery polymer (a-1) synthetic, make above-mentioned composition polymerization 9 hours.The result obtains a kind of conjugated diene rubber shape multipolymer (d-1) latex, and monomer conversion is 97%, and its granularity is 0.08 μ m, and gel content is 80% (weight).
Contain the synthetic of acidic group multipolymer (i-1) latex
2.5 parts of potassium oleates
2.5 parts in dioctyl sulfo-succinic acid potassium
Disodium EDTA. 0.012 part of dihydrate
Ferrous sulfate. 0.004 part of heptahydrate
0.5 part of rongalite
200 parts of distilled water
Above-mentioned composition is packed in one 5 liters the separable glass flask.Stir down with nitrogen and replace oxygen in the system, and content is heated to 70 ℃.The following mixture of removing oxygen with nitrogen is added dropwise to wherein, 4 hours by a definite date, carries out polymerization.
85 parts of n-butyl acrylates
15 parts of methacrylic acids
0.5 part of cumene hydroperoxy-
At 70 ℃ reaction mixture was kept 1 hour, to obtain a kind of acidic group multipolymer (i-1) latex that contains, transformation efficiency is 97%.
Contain the synthetic of acidic group multipolymer (i-2)
Be bonded into the same way as that contains acidic group multipolymer (i-1) latex and carry out herein polymerization, different is, the monomer mixture of dropping is formed and made the following changes.The result has obtained a kind of acidic group multipolymer (i-2) latex that contains, and the monomer whose transformation efficiency is 96%.
80 parts of n-butyl acrylates
20 parts of methacrylic acids
0.5 part of cumene hydroperoxy-
Synthesizing of graft copolymer (A-1)
In 20 liters of separable flasks, add 50 parts of (as solid ingredient) rubbery copolymers (a-1) latex, add a kind of aqueous solution that 0.4 part (as solid ingredient) contains 10% sodium sulfate again under stirring.Add 1.3 parts (as solid ingredients) again and contain acidic group multipolymer (i-1) latex.Content was kept 30 minutes, add 95 parts of distilled water again.Obtain a kind of agglomerative rubbery copolymer (a '-1) latex, its median size is 0.27 μ m.
1.25 parts of the sodium salts of N-Sarkosyl L
Disodium EDTA. 0.003 part of dihydrate
0.001 part of ferrous sulfate heptahydrate
0.5 part of rongalite
Above-mentioned composition is added, and stirring down, content is heated to 75 ℃.Splash into following monomer mixture with 120 minutes, to carry out graft polymerization.
15 parts of vinyl cyanide
35 parts of vinylbenzene
0.3 part of the tert-butylhydroperoxide
0.1 part in n-octyl mercaptan
After dripping monomer mixture, reaction mixture was kept 1 hour, to obtain a kind of graft copolymer latex.By this graft copolymer latex is added in the moisture dilute sulphuric acid, dehydration, washing and dryly solidify making it, obtain a kind of graft copolymer (A-1).
Synthesizing of graft copolymer (A-2)
Repeat the building-up process of graft copolymer (A-1), until having obtained the agglomerative rubbery copolymer.
Agglomerative rubbery copolymer (a '-1)
60 parts in latex (as solid ingredient)
0.75 part of the sodium salt of N-lauroyl sarcosine
Disodium EDTA. 0.0015 part of dihydrate
Ferrous sulfate. 0.0005 part of heptahydrate
0.4 part of rongalite
With the above-mentioned composition 20 liters of separable flasks of packing into, stir down content is heated to 75 ℃.With 90 minutes following monomer mixture is added in the foregoing thing, to carry out graft polymerization.
36 parts of methyl methacrylates
4 parts of ethyl propenoates
0.15 part of cumene hydroperoxy-
0.05 part in n-octyl mercaptan
After dripping this monomer mixture, reaction mixture was further kept 1 hour, obtain a kind of graft copolymer latex.By this graft copolymer latex is added in the moisture dilute sulphuric acid, dehydration, washing are also dry and make it to solidify, and obtain a kind of graft copolymer (A-2).
Synthesizing of graft copolymer (A-3)
Press the same way as of synthesising graft copolymer (A-1), obtain a kind of graft copolymer (A-3), different is, adopt rubbery copolymer (a-2) as rubbery polymer, and adopt and contain acidic group polymkeric substance (i-2) and replace the original used acidic group multipolymer (i-1) that contains in the gelatinization process as jelling agent.The mean particle size of the rubbery copolymer after the gelling (a '-2) is 0.31 μ m.
Synthesizing of compound rubbery polymer (b '-1)
In 20 liters of separable flasks, pack into rubbery polymer (d-1) latex of 20 parts (as solid ingredients).Stirring down, adding 0.5 part (as solid ingredient) contains acidic group multipolymer (i-2) latex.Content was kept 30 minutes, add 160 parts of distilled water again, to finish gelatinization process.The result obtains the agglomerative rubbery copolymer that mean particle size is 0.37 μ m.
79.55 parts of n-butyl acrylates
0.3 part of allyl methacrylate(AMA)
0.15 part of Ethylene glycol dimethacrylate
0.2 part of the tert-butylhydroperoxide
Add above-mentioned monomer mixture, fully stir content.The sodium salt that in reactive system, adds 0.5 part of N-bay acidic group sarkosine, and rinse out oxygen in the system with nitrogen.Temperature rise to 45 ℃ in making, and form below adding.
0.5 part of rongalite
Ferrous sulfate. 0.0003 part of heptahydrate
Disodium EDTA. 0.0009 part of dihydrate
10 parts of distilled water
Consequently, polymerization is initiated, and interior temperature rise is to about 70 ℃.Stir and 75 ℃ under, make reaction mixture maintenance 90 minutes, obtain a kind of compound rubbery polymer (b '-1) latex.The gel content of having measured it is 84% (weight).
Synthesizing of compound rubbery polymer (b '-2)
Repeat the building-up process of compound rubbery polymer (b '-1), different is that 0.2 part of n-octyl mercaptan of adding obtains a kind of compound rubbery polymer (b '-2) to be used for seeding polymerization in this monomer mixture.
Its gel content is 47% (weight).
Synthesizing of graft copolymer (B-1)
Compound rubbery polymer (b '-1) latex
(as solid ingredient) 50 parts
1.2 parts of the sodium salts of N-lauroyl sarcosine
0.4 part of rongalite
Ferrous sulfate. 0.001 part of heptahydrate
Disodium EDTA. 0.003 part of dihydrate
100 parts of distilled water
Above-mentioned composition is packed in 20 liters of separable flasks, stir down heating content to 75 ℃.With 120 minutes dropping following monomer mixture, to carry out graft polymerization.
15 parts of vinyl cyanide
35 parts of vinylbenzene
0.3 part of the tert-butylhydroperoxide
0.1 part in n-octyl mercaptan
Add after this monomer mixture, reaction mixture under agitation kept 1 hour, obtained a kind of graft copolymer latex.This graft copolymer latex is added in the moisture dilute sulphuric acid, make it to solidify, dewater, wash and drying, obtain a kind of Powdered graft copolymer (B-1).
Synthesizing of graft copolymer (B-2)
Repeat the building-up process of graft copolymer (B-1), different is with compound rubbery polymer (b '-2) replacement compound rubbery polymer (b '-1), to obtain a kind of graft copolymer (B-2).
Synthesizing of compound rubbery polymer (c '-1)
1 part of Witco 1298 Soft Acid
1 part of Sodium dodecylbenzene sulfonate
200 parts of distilled water
Have the mixture of siloxanes of forming below and be added in the above-mentioned composition a kind of, 10, pre-mixing under the 000rpm is 300kg/cm at pressure with a mixing tank
2Carry out emulsification and dispersion down, obtain a kind of organo-siloxane latex with a homogenizer.
1.0 parts of tetraethoxy-silicanes
γ-iso-butylene acyl-oxygen base propyl group diformazan
0.25 part of oxygen ylmethyl silicomethane
48.75 parts of octamethylcyclotetrasiloxanes
This mixture solution is transferred in 20 liters of separable flasks, in 80 ℃ of heating 5 hours, left standstill 48 hours in 20 ℃ again under stirring.With aqueous sodium hydroxide solution this latex being neutralized to PH is 7.5, obtains a kind of organopolysiloxane rubbery polymer (C-1) latex, and its mean particle size is 0.16 μ m.In this latex, add 70 parts of distilled water, stir adding following monomer mixture down, make it thorough mixing.
48.6 parts of n-butyl acrylates
1.05 parts of allyl methacrylate(AMA)s
0.35 part of Ethylene glycol dimethacrylate
0.3 part of the tert-butylhydroperoxide
With oxygen in the nitrogen scavenge system, with interior temperature rise to 50 ℃.In following mixture adding system, initiated polymerization thus.
0.3 part of rongalite
Ferrous sulfate. 0.002 part of heptahydrate
Disodium EDTA. 0.006 part of dihydrate
10 parts of distilled water
As its result, interior temperature rise makes this reaction mixture keep 2 hours at 70 ℃ to about 65 ℃ then, obtains a kind of compound rubbery polymer (C '-1) latex.Having measured gel content is 95% (weight).
Synthesizing of compound rubbery polymer (C '-2)
Repeat the building-up process of compound rubbery polymer (C '-1), different is, has adopted the following monomer mixture that is used for seeding polymerization, has obtained a kind of compound rubbery polymer (C '-2).Having measured its gel content is 63% (weight).
49.7 parts of n-butyl acrylates
0.35 part of allyl methacrylate(AMA)
0.3 part of the tert-butylhydroperoxide
0.3 part in n-octyl mercaptan
Synthesizing of graft copolymer (C-1)
Compound rubbery polymer (C '-1)
60 parts in latex (as solid ingredient)
0.3 part of Sodium dodecylbenzene sulfonate
80 parts of distilled water
Above-mentioned composition is added in one 20 liters the separable flask.Stir down content is heated to 70 ℃, wherein drip following monomer mixture with 60 fens clockwise, to carry out graft polymerization.
12 parts of vinyl cyanide
28 parts of vinylbenzene
0.2 part of cumene hydroperoxy-
0.1 part of uncle's lauryl mercaptan
After adding this monomer mixture, under stirring this reaction mixture was kept 2 hours, obtain a kind of graft copolymer latex.This graft copolymer latex is put into calcium chloride water make it to solidify, dehydration, washing and dry obtains a kind of powdered graft copolymer (C-1).
Synthesizing of graft copolymer (C-2)
Repeat the building-up process of graft copolymer (C-1), different is with compound rubbery polymer (C '-2) replacement compound rubbery polymer (C '-1), to obtain a kind of graft copolymer (C-2).
Synthesizing of graft copolymer (D-1)
In the separable flask of one 20 liters of 60 parts of (as solid ingredient) conjugated diene rubber shape multipolymers (d-1) latex addings, under agitation contain acidic group multipolymer (i-1) latex again to wherein adding 1.2 parts (as solid ingredients), under stirring content was kept 30 minutes, add 80 parts of distilled water again.The result obtains a kind of agglomerative rubbery copolymer (d '-1) latex that mean particle size is 0.28 μ m.
0.4 part in the rhodium acid potassium of disproportionation
Trisodium phosphate. 0.02 part of decahydrate
Ferrous sulfate. 0.005 part of heptahydrate
Dextran 10 .4 part
0.02 part in sodium hydroxide
Above-mentioned composition is added wherein, under stirring with this mixture heating up to 60 ℃.With 120 minutes following monomer mixture is added drop-wise in this mixture, carries out graft polymerization.
12 parts of vinyl cyanide
28 parts of vinylbenzene
0.2 part of cumene hydroperoxy-
0.4 part of uncle's lauryl mercaptan
After dripping this monomer mixture, reaction mixture was kept 1 hour again, obtain a kind of graft copolymer latex.Place a kind of moisture dilute sulphuric acid to make it to solidify it, dehydration, washing and dry obtain a kind of graft copolymer (D-1).
Synthesizing of rigid thermoplastic resin (III-1)
30 parts of vinyl cyanide
70 parts of vinylbenzene
0.15 part of azobis isobutyronitrile
0.4 part of uncle's lauryl mercaptan
0.5 part in calcium phosphate
150 parts of distilled water
Above-mentioned composition is packed in 100 liters of autoclaves into vigorous stirring.After in reactive system, having formed dispersion, reaction mixture is heated to 75 ℃, and polyase 13 hour.Reaction mixture is heated to 110 ℃ then, through 30 minutes, cooling, dehydration, washing and dry obtain a kind of pulverous rigid thermoplastic resin (III-1).
Synthesizing of rigid thermoplastic resin (III-2)
20 parts of vinyl cyanide
40 parts of vinylbenzene
40 parts of methyl methacrylates
0.15 part of azobis isobutyronitrile
0.2 part of uncle's lauryl mercaptan
0.5 part in calcium phosphate
150 parts of distilled water
Identical process by synthetic rigid thermoplastic resin (III-1) makes above-mentioned composition polymerization, obtains a kind of powdery rigid plastic resin (III-2).
Synthesizing of rigid thermoplastic resin (III-3)
3 parts of potassium oleates
Dextran 10 .5 part
Ferrous sulfate. 0.005 part of heptahydrate
Trisodium phosphate. 0.5 part of decahydrate
0.15 part of anhydrous sodium sulphate
200 parts of distilled water
10 parts of vinyl cyanide
70 parts of alpha-methyl styrenes
0.1 part of uncle's lauryl mercaptan
Above-mentioned composition packed into one serves as a contrast 20 liters of polymerization reactors of glass, and under agitation is heated to 60 ℃.Add 0.5 part of cumene hydroperoxy-, carry out polymerization thereby drip 20 parts of vinyl cyanide with 120 fens clock times again.In the polymerization, interior temperature rises to 80 ℃ gradually.At 80 ℃ reaction mixture was kept 2 hours subsequently, obtain a kind of copolymer emulsion.This copolymer emulsion is put into magnesium sulfate solution make it to solidify, dehydration, washing and dry obtain a kind of powdered rigid thermoplastic resin (III-3).
Synthetic rigid thermoplastic resin (III-4)
40 parts of vinylbenzene
10 parts of methylethylketones
With vacuum pump 50 liters of polymerization reactors of complete mixed type glass lined are found time, and charge into nitrogen inward, this operation repeats several times, and said mixture is added in the reactor of nitrogen atmosphere protection.Content is heated to 100 ℃, and following mixture is added drop-wise in the polymerization reactor with 60 minutes time, to carry out solution polymerization:
20 parts of vinyl cyanide
10 parts of N-phenylmaleimides
1,1-dibutyl peroxide-3,3,0.07 part of 5-trimethyl-cyclohexane
20 parts of methylethylketones
After mixture dropwises, with reaction mixture in 100 ℃ aging 1 hour, with the residual content of remarkable reduction N-phenylmaleimide.A kind of polymerization starter is placed reaction mixture, and cooling rapidly then afterwards, utilizes toothed gear pump that polymerization reaction mixture is added in the degassing forcing machine quantitatively, removes remaining monomer, organic solvent or the like.Then, extrude multipolymer, and handle, obtain rigid thermoplastic resin (III-4) particle with tablets press with rope form.
The preparation thermoplastic resin composition
Graft copolymer (I), graft copolymer (II) and the rigid thermoplastic resin (III) of predetermined amount are placed the Hensehel mixing machine and carry out blend with following composition.
Adeka Stab AO-20 (trade(brand)name,
Asahi Demka K.K product) 0.3 part
Adeka Stab AO-4412S (trade(brand)name,
Asahi Denka K.K product) 0.3 part
1 part of ethylenebis stearylamide
0.3 part of calcium stearate
SH200 (trade(brand)name of silicone oil, Dow
Corning Toray Silicone Ca Ltd product) 0.03 part
With screw extrusion press with said mixture in 220-260 ℃ of melt kneading, and use the tablets press granulation, utilize injection moulding machine or plasticator to form various samples.
The resin combination that adopts following method evaluation to obtain thus.(1) cantilever-type impact strength (IZ): measure (unit of measure: kg.cm/cm) according to ASTMD-256.
(2) Rockwell hardness (R): measure (R scale) according to ASTM D-785.
(3) vicat softening temperature (VST): measure (unit of measure: ℃) according to ISO R-306.
(4) chemical proofing: from the holoplast of the thick resin combination of 2mm, cutting-out is of a size of the sample of 35 * 120mm and sample is contained in (main shaft: 120mm, little axle: 40mm) on the 1/4 oval anchor clamps.Sample is coated with the last layer pharmaceutical chemicals, coats the layer of polyethylene film, and be exposed to this pharmaceutical chemicals following 4 hours in 25 ℃.For the lower boiling pharmaceutical chemicals, test by the following method, sample is placed in the moisture eliminator with shut-off valve with anchor clamps, and was exposed to this pharmaceutical chemicals following 24 hours in 250 ℃, charge into its steam in the moisture eliminator simultaneously.After the exposure, observe the condition of surface of sample, and will not form the index of fissured maximum stress strain value as this resin combination chemical proofing.
Following material is used as pharmaceutical chemicals:
1,1-two chloro-1-fluoroethanes
Brake solution (trade(brand)name 2400G, Toyota Motor Co. produces)
Dewaxing medium (Ltd. produces for trade(brand)name ST-7, Yushiro Chemical Industry)
Salad oil (Nisshin Oil Co.Ltd. product)
Dioctyl phthalate (DOP)
Table 1
Resin combination
Graft copolymer (I) graft copolymer (II) rigid thermoplastic rubber-like polyacrylic acid alkane
Resin (III) compound content base ester units #
Content
(part) (part) (part) (wt.%) (wt.%) embodiment .1 A-1 (44) D-1 (10) III-1 (46) 28 39 embodiment .2 A-2 (35) D-1 (10) III-2 (55) 27 39 embodiment .3 B-1 (30) D-1 (15) III-1 (55) 24 50 contrast real .1 A-1 (10) D-1 (35) III-1 (55) 26 10 is executed example " .2 B-1 (70) D-1 (10) III-1 (20) 41 68 " .3 B-1 (15) D-1 (5) III-1 (80) 11 57 " .4 A-3 (44) D-1 (10) III-1 (46) 28 79 embodiment .4 C-1 (44) D-1 (10) III-1 (46) 28 39
Physical property chemical proofing (critical strain %)
Iz R VST 1,1-two O-phthalics
Chloro-1-fluorine brake solution dewaxing medium salad oil dioctyl phthalate
Ethane embodiment .1 39 92 95 1.8 0.6 1.1 1.0 0.8 embodiment .2 34 96 99 1.9 0.6 1.0 1.0 0.8 embodiment .3 32 97 98 2.0 0.6 1.1 1.0 0.9 contrasts are real
.1 38 96 97＜0.3＜0.3 0.3 0.3＜0.3 execute example " .2 48 76 81 〉=2 1.2 〉=2 〉=2 1.6 " .3 10 109 99 1.0 0.3 0.6 0.6 0.4 " .4 15 90 94 2.0 0.8 1.4 1.8 1.2 embodiment .4 31 94 96 1.9 0.7 1.0 1.1 0.8
Annotate: the * numeral is rounded up to the content in the 100wt.% resin combination behind first decimal.The # numeral is rounded up to
The content of the alkyl acrylate behind first decimal in the 100wt.% rubbery polymer.
Table .2
Resin combination
Graft copolymer (I) graft copolymer (II) rigid thermoplastic rubber-like polyacrylic acid alkane
Resin (III) compound content base ester units #
Content
(part) (part) (part) is (wt.%) (wt.%)
Embodiment .5 B-1 (28) D-1 (10) III-1 (62) 20 56
Embodiment 6 C-1 (36) D-1 (10) III-1 (54) 24 38 comparative example .5 B-2 (28) D-1 (10) III-1 (62) 20 56
Contrast real .6 C-2 (36) D-1 (10) III-1 (54) 24 38
Execute example
Physical property chemical proofing (critical strain %)
Iz R VST 1,1-two O-phthalics
Chloro-1-fluorine brake solution dewaxing medium salad oil dioctyl phthalate
Ethane
Embodiment .5 28 100 98 1.9 0.6 1.0 1.0 0.8
Embodiment .6 24 98 97 1.6 0.7 1.0 1.0 0.8 comparative example .5 18 99 98 1.9 0.5 1.1 1.0 0.8
Contrast is real
.6 10 96 97 1.5 0.6 0.9 1.0 0.7
Execute example
Annotate: the * numeral is rounded up to the content in the 100wt.% resin combination behind first decimal.The # numeral is rounded up to
The content of the alkyl acrylate behind first decimal in the 100wt.% rubbery polymer.
Table .3
Resin combination
Graft copolymer (I) graft copolymer (II) rigid thermoplastic rubber-like polyacrylic acid alkane
Resin (III) compound content base ester units #
Content
(part), (part), (part), (wt.%), (wt.%) embodiment .7 A-2, (40) D-1, (5) III-3, (55) 27 44 embodiment .8 B-1, (40) D-1, (10) III-3, (50) 26 62 embodiment .9 B-1, (40) D-1, (10) III-4, (50) 26 62 contrasts are real
7 A-3 (40) D-1 (10) III-3 (55) 26 77 executes example
Physical property chemical proofing (critical strain %)
Iz R VST 1,1-two O-phthalics
Chloro-1-fluorine brake solution dewaxing medium salad oil dioctyl phthalate
Example is executed in ethane embodiment .7 16 98 114 〉=2 0.7 1.1 1.0 0.8 embodiment .8 19 98 112 〉=2 0.7 1.1 1.1 0.8 embodiment .9 18 99 113 〉=2 0.8 1.2 1.2 0.9 contrast real .7 5 96 112 〉=2 0.8 1.2 1.1 0.8
Annotate: the * numeral is rounded up to the content in the 100wt.% resin combination behind first decimal.The # numeral is rounded up to
The content of the alkyl acrylate behind first decimal in the 100wt.% rubbery polymer.
Can draw to draw a conclusion by table 1.
Resistance to impact shock and all good thermoplastic resin composition of chemical proofing in embodiments of the invention 1-4, have been obtained.Otherwise because the thermoplastic resin in the comparative example 1 is compared with the present invention, acrylic acid alkyl ester units content reduces in rubbery polymer, and this resin combination demonstrates relatively poor chemical proofing.Because thermoplastic resin composition and the rubbery polymer that contains high level of comparing of the present invention in the comparative example 2, the Rockwell hardness of this resin combination is lower than 80, and has softer surface.By contrast, because thermoplasticity oil/fat composition and the rubbery polymer that contains lower aq of comparing of the present invention in the comparative example 3, the resistance to impact shock of this resin combination is relatively poor.In comparative example 4, the unitary content of alkyl acrylate of rubbery polymer and thermoplastic resin is consistent with the amount that the present invention limits.Yet because use therein traditional AAS resin, its rubbery polymer is simple butyl acrylate rubber, and the resistance to impact shock of this resin combination is relatively poor.
In addition, by table 2 it can be asserted that: because the graft copolymer (I) of the thermoplastic resin composition in the comparative example 5 and 6 contains the compound rubbery polymer of low-gel content, this resin combination shows relatively poor resistance to impact shock.
Have again, by table .3 it can be asserted that: even when using heat-stable rigid thermoplastic resin (III), wherein used the thermoplasticity oil/fat composition of the present invention of reception multipolymer (I) to compare, also had very high resistance to impact shock with the resin combination in the comparative example 7 that has used AAS resin.
The invention provides a kind of graft copolymer, the graft copolymer that obtains by monomer mixture and conjugated-diolefin rubber graft polymerization and rigid thermoplastic resin by obtaining by monomer mixture and the polymerization of alkyl acrylate grafting rubbers by optimum proportion mixed the thermoplastic resin composition.This thermoplastic resin composition's chemical proofing and resistance to impact shock are extremely good.So thermoplastic resin composition of the present invention is very suitable to the electrical part that contacts with polyurethane foams, various oils, washing composition etc. and the component of vehicle.
Claims (13)
- One kind by with following base stock, composition that to be graft copolymer (I) and graft copolymer (II) mix to make with following rigid thermoplastic resin (III):(I) graft copolymer (I), it is the graft copolymer of at least a alkyl acrylate rubber and is selected from following graft copolymer (A), (B) and (C):(A) graft copolymer (A), it is by vinyl cyanide and the cinnamic monomer mixture of 55-85% (weight) that 20 to 80 parts (weight) is contained 15-45% (weight) or contains 80-100% (weight) alkyl methacrylate and the monomer mixture of the alkyl acrylate of 0-20% (weight), 20-80 part (weight) as the elastomeric multipolymer of the gelling of solid ingredient (a ') latex in the presence of graft polymerization make, median size that should (a ') latex is 0.15 to 0.5 μ m, its polymkeric substance (i) latex by will containing acidic group and oxygen acid metal-salt (ii) are added in elastomeric polymkeric substance (a) latex and make, the gel content that is somebody's turn to do (a) latex is greater than 70% (weight) and by the alkyl acrylate with 35-85% (weight), the conjugated diolefine of 15-65% (weight) and 0-20% (weight) can make with the monomer emulsion polymerization of these compound polymerizations(B) graft copolymer (B), it is by 20-80 part (weight) being contained 15-45% (weight) vinyl cyanide, the cinnamic monomer mixture of 55-85% (weight), make in the presence of 20-80 part (weight) as the compounded rubber shaped polymer of solid ingredient (b ') latex, gel content that should (b ') latex is greater than 70% (weight), and by 35-95% (weight) is contained alkyl acrylate and with the polymerisable monomeric monomer mixture of this alkyl acrylate 5-65% (weight) as conjugated diene rubber shaped polymer (b) latex of solid ingredient in the presence of graft polymerization make and(C) graft copolymer (C), it is by 20-80 part (weight) being contained the vinyl cyanide of 15-45% (weight) and the cinnamic monomer mixture of 55-85% (weight), 20-80 part (weight) as the compounded rubber shaped polymer of solid ingredient (C ') latex in the presence of graft polymerization make, gel content that should (c ') latex greater than 70% (weight) and by 35-95% (weight) is contained alkyl acrylate and polymerisable therewith monomeric monomer mixture 5-65% (weight) as organopolysiloxane rubbery polymer (C) latex of solid ingredient in the presence of seeding polymerization make;(II) graft copolymer, it is by vinyl cyanide that 30-70 part (weight) is contained 15-45% (weight) and the cinnamic monomer mixture of 55-85% (weight), 30-70 part (weight) as the elastomeric multipolymer of the gelling of solid ingredient (d ') latex in the presence of graft polymerization make, average footpath that should (d ') latex is 0.15-0.5 μ m, make in polymkeric substance (d) latex that polymkeric substance (i) latex by will containing acidic group and non-imposed oxygen acid metal-salt (ii) are added to the conjugated diene rubber shape, median size that should (d) latex be 0.03-0.2 μ m and by with the conjugated diolefine of 70-100% (weight) and 0-30% therewith the monomer emulsion polymerization of copolymerization make;(III) rigid thermoplastic resin (III), it is selected from following monomer by at least 2 kinds of polymerizations and makes: vinyl cyanide, vinylbenzene, unsaturated ester and maleimide compound; Wherein the described thermoplastic resin composition of 100% (weight) contains the rubbery polymer of 15-30% (weight), and the rubbery polymer of 100% (weight) contains the acrylic acid alkyl ester units of 30-85% (weight).
- 2. according to the described thermoplastic resin composition of claim 1, wherein graft copolymer (I), graft copolymer (II) and rigid thermoplastic resin (III) mix by this way, so that the described thermoplastic resin composition of 100% (weight) is contained 20-28% (weight) rubbery polymer, and contain 30-85% (weight) acrylic acid alkyl ester units in the rubbery polymer of 100% (weight).
- 3. according to the described thermoplastic resin composition of claim 1, wherein said rigid thermoplastic resin (III) is a kind of copolymer resin that obtains by polymerization 20-45% (weight) vinyl cyanide and 55-80% (weight) vinylbenzene.
- 4. according to the described thermoplastic resin composition of claim 1, wherein said rigid thermoplastic resin (III) is a kind of copolymer resin that obtains by polymerization 25-40% (weight) vinyl cyanide and 60-75% (weight) vinylbenzene.
- 5. according to the described thermoplastic resin composition of claim 1, wherein said rigid thermoplastic resin (III) is a kind of copolymer resin that obtains by polymerization 10-40% (weight) vinyl cyanide, 30-50% (weight) vinylbenzene and 30-50% (weight) alkyl methacrylate, and its total amount is 100% (weight).
- 6. according to the described thermoplastic resin composition of claim 1, wherein said rigid thermoplastic resin (III) is a kind of by copolymer-1 0-40% (weight) vinyl cyanide, 40-80% (weight) vinylbenzene and 5-40% (weight) maleimide compound and the copolymer resin that obtains, its total amount is 100% (weight).
- 7. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (B) employing median size is that conjugated-diolefin rubber shaped polymer (b) latex of 0.2-1.0 μ m obtains.
- 8. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (A) is a kind of by adopting graft polymerization to contain the graft copolymer that 20-35% (weight) vinyl cyanide and the cinnamic monomer mixture of 65-80% (weight) obtain.
- 9. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (B) is a kind of by adopting graft polymerization to contain the graft copolymer that 20-35% (weight) vinyl cyanide and the cinnamic monomer mixture of 65-80% (weight) obtain.
- 10. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (C) is a kind of by adopting graft polymerization to contain the graft copolymer that 20-35% (weight) vinyl cyanide and the cinnamic monomer mixture of 65-80% (weight) obtain.
- 11. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (II) is a kind of by adopting graft polymerization to contain the graft copolymer that 20-35% (weight) vinyl cyanide and the cinnamic monomer mixture of 65-80% (weight) obtain.
- 12. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (B) is a kind of graft copolymer that obtains by the monomer mixture that contains 95-99.95% (weight) alkyl acrylate and 0.05-5% (weight) linking agent and graft crosslinking agent with the polymerization of conjugated-diolefin rubber shaped polymer (b) latex grafting.
- 13. according to the described thermoplastic resin composition of claim 1, wherein said graft copolymer (C) is to obtain by the monomer mixture that contains 95-99.95% (weight) alkyl acrylate and 0.05-5% (weight) linking agent and graft crosslinking agent with the polymerization of organopolysiloxane rubbery polymer (C) latex grafting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP102985/93 | 1993-04-28 | ||
| JP10298593 | 1993-04-28 |
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| CN1099775A CN1099775A (en) | 1995-03-08 |
| CN1057548C true CN1057548C (en) | 2000-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94105231A Expired - Lifetime CN1057548C (en) | 1993-04-28 | 1994-04-28 | Thermoplastic resin composition |
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| Country | Link |
|---|---|
| US (2) | US5889113A (en) |
| KR (1) | KR100295484B1 (en) |
| CN (1) | CN1057548C (en) |
| DE (1) | DE4414762B4 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108342C (en) * | 1995-12-14 | 2003-05-14 | 奇美实业股份有限公司 | Thermoplastic resin composite |
| JP3376283B2 (en) * | 1998-07-14 | 2003-02-10 | 三菱レイヨン株式会社 | Acrylic rubber-based impact strength modifier and hard vinyl chloride-based resin composition using the same |
| DE10058133A1 (en) * | 2000-11-22 | 2002-05-23 | Basf Ag | Rubber containing thermoplastic molding compositions useful for production of injection molded parts comprises at least one elastic rubber polymerisate and at least one thermoplastic polymer |
| CN1307257C (en) * | 2000-12-25 | 2007-03-28 | 三菱丽阳株式会社 | Graft copolymer and thermoplastic resin composition |
| KR100789597B1 (en) * | 2001-03-28 | 2007-12-27 | 테크노 폴리머 가부시키가이샤 | Rubber-Reinforced Thermoplastic Resin and Rubber-Reinforced Thermoplastic Resin Composition |
| CN100429272C (en) * | 2002-04-30 | 2008-10-29 | 株式会社钟化 | Polyorganosiloxane-containing graft copolymer composition |
| DE60328614D1 (en) * | 2002-10-01 | 2009-09-10 | Kaneka Corp | TRANSPARENT AND HITCH THERMOPLASTIC RESIN COMPOSITION |
| US20050176894A1 (en) * | 2004-02-05 | 2005-08-11 | Jeong Yang-Seung | Method of emulsion polymerization using liquid miniemulsion as seed particle |
| KR101126016B1 (en) * | 2005-10-04 | 2012-03-19 | 주식회사 엘지화학 | Method for preparing graft rubber latex having low residual monomer content |
| WO2009011280A1 (en) * | 2007-07-13 | 2009-01-22 | Mitsubishi Rayon Co., Ltd. | Graft copolymer, thermoplastic resin composition, and molded object |
| EP2042530A1 (en) * | 2007-09-26 | 2009-04-01 | Eliokem | Rubbery polymer with low compression set |
| JP5323385B2 (en) * | 2008-01-30 | 2013-10-23 | 東京応化工業株式会社 | Adhesive composition and adhesive film |
| JP5368845B2 (en) * | 2008-06-17 | 2013-12-18 | 東京応化工業株式会社 | Adhesive composition, adhesive film, and heat treatment method |
| CN103421268B (en) * | 2012-05-15 | 2016-04-06 | 中国石油天然气股份有限公司 | Easy processed-type ABS resin composition and method of making the same |
| KR101905939B1 (en) | 2015-08-31 | 2018-10-08 | 주식회사 엘지화학 | Thermoplastic resin composition and method for preparing the same |
| KR101965480B1 (en) * | 2016-09-29 | 2019-04-03 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| SG11202002766WA (en) * | 2017-09-29 | 2020-04-29 | Sekisui Chemical Co Ltd | Foamed resin molded article |
| US20220065535A1 (en) * | 2020-08-28 | 2022-03-03 | Res Polyflow Llc | Plastic conversion feed system |
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| CN86100992A (en) * | 1985-02-08 | 1987-08-19 | 采煤化学公司 | Thermoplastic composite and production method thereof and goods |
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| JPS58179257A (en) * | 1982-04-13 | 1983-10-20 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| US4585832A (en) * | 1983-06-23 | 1986-04-29 | Mitsubishi Monsanto Chemical Company | Weather and impact resistant resin composition and process for its preparation |
| JPS6036553A (en) * | 1983-08-09 | 1985-02-25 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JPH0725973B2 (en) * | 1984-04-28 | 1995-03-22 | 三菱レイヨン株式会社 | Impact resistant thermoplastic resin composition |
| JPS62181312A (en) * | 1986-02-06 | 1987-08-08 | Mitsubishi Rayon Co Ltd | Production of thermoplastic resin composition having improved impact resistance, weather resistance and moldability |
| JP2608439B2 (en) * | 1988-01-25 | 1997-05-07 | 三菱レイヨン株式会社 | Impact resistant resin composition |
| DE3839588A1 (en) * | 1988-11-24 | 1990-05-31 | Bayer Ag | POLYMER PANEL SYSTEMS WITH GOOD AGING RESISTANCE |
| JP3090942B2 (en) * | 1990-11-02 | 2000-09-25 | 三菱化学株式会社 | Thermoplastic resin composition for refrigerator inner box and refrigerator inner box obtained by molding the same |
| DE4122871A1 (en) * | 1990-11-29 | 1992-06-04 | Bayer Ag | ABS MOLDS |
| DE4230257A1 (en) * | 1992-09-10 | 1994-03-17 | Basf Ag | Molding compound |
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1994
- 1994-04-27 DE DE4414762A patent/DE4414762B4/en not_active Expired - Lifetime
- 1994-04-28 CN CN94105231A patent/CN1057548C/en not_active Expired - Lifetime
- 1994-04-28 KR KR1019940009087A patent/KR100295484B1/en not_active IP Right Cessation
-
1997
- 1997-07-28 US US08/901,328 patent/US5889113A/en not_active Expired - Lifetime
- 1997-10-20 US US08/953,535 patent/US5872184A/en not_active Expired - Lifetime
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| CN86100992A (en) * | 1985-02-08 | 1987-08-19 | 采煤化学公司 | Thermoplastic composite and production method thereof and goods |
| CN1033282A (en) * | 1987-11-02 | 1989-06-07 | 斯塔米卡本公司 | Thermoplastic elastomer mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1099775A (en) | 1995-03-08 |
| DE4414762A1 (en) | 1994-11-03 |
| US5889113A (en) | 1999-03-30 |
| DE4414762B4 (en) | 2009-02-12 |
| US5872184A (en) | 1999-02-16 |
| KR100295484B1 (en) | 2001-10-24 |
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